CN114797497A - Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application - Google Patents
Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application Download PDFInfo
- Publication number
- CN114797497A CN114797497A CN202210596788.1A CN202210596788A CN114797497A CN 114797497 A CN114797497 A CN 114797497A CN 202210596788 A CN202210596788 A CN 202210596788A CN 114797497 A CN114797497 A CN 114797497A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- alpo
- sieve membrane
- alcohol
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 94
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000001133 acceleration Effects 0.000 title claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 2
- 239000010457 zeolite Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/105—Removal of contaminants of nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of preparation and application of molecular sieve membrane materials, and provides a method for preparing an AlPO-18 molecular sieve membrane by alcohol acceleration and application thereof. The invention adds alcohol into the initial gel to prepare AlPO-18 molecular sieve membrane, in practical operation, the synthesis time of AlPO-18 molecular sieve membrane can be shortened, and the membrane prepared by the method has good CO 2 /CH 4 And N 2 /CH 4 Separation performance.
Description
Technical Field
The invention relates to the technical field of preparation and application of molecular sieve membrane materials, in particular to a method for preparing an AlPO-18 molecular sieve membrane by alcohol acceleration and application thereof.
Background
With the continuous increase of the world population and economy, the global energy demand is remarkably increased, the emission amount of greenhouse gases and harmful substances is increased, and the energy problem and the environmental problem are increasingly urgent. In recent years, new energy sources such as solar energy, wind energy and the like are rapidly developed, and the method has a good application prospect. Nevertheless, fossil energy such as coal, oil and natural gas is still the most widely used energy at present, and unlike coal and oil with limited reserves, the natural gas reserves are very abundant, and the fossil energy is a clean energy with higher calorific value, and has considerable development potential. However, natural gas contains CO 2 、N 2 And the like, which significantly reduces the calorific value thereof, and thus purification treatment is an indispensable step for efficient utilization of natural gas. The membrane separation technology has the advantages of energy consumption saving, environmental protection, high efficiency, simple and convenient operation and the like, and is one of the very important technologies in the current separation process.
At present, the materials used for membrane separation are mainly polymers and inorganic materials. The polymer film has the advantages of low cost, strong plasticity, easy amplification and the like, but has the defects of unstable chemical property and structure, thereby easily causing the reduction of the separation performance. The inorganic molecular sieve membrane material has good chemical and thermal stability, and uniform and rigid pore channels can realize the separation of molecular level, so the inorganic molecular sieve membrane material has application prospect in the field of natural gas purification. AlPO-18 is a compound of AlO 4 - And PO 4 + The phosphorus-aluminum molecular sieve material with AEI framework structure formed by connecting tetrahedra through oxygen atoms has eight-membered ring cross channels with the diameter of 0.38nm and 15.1T/nm 3 Low skeletal density of (C), separation of CH 4 (kinetic diameter: 0.38nm), CO 2 (kinetic diameter: 0.33nm), N 2 (kinetic diameter: 0.36nm) systems have great potential for use.
Most of the current reports on AlPO-18 molecular sieve membranes for gas separation applications use tetraethylammonium hydroxide (TEAOH) as a template for preparation synthesis, however, the membraneThe plate agent is expensive and is not beneficial to the large-scale preparation of the AlPO-18 molecular sieve membrane. In recent years, inexpensive N, N-Diisopropylethylamine (DIPEA) has also been used for the synthesis of AlPO-18 molecular sieve membranes, such as the literature [ Wu T, Tanaka K, Chen X S, et al].Membrane,2018,43(2),67-73.]Hydrothermal reaction at 205 deg.c for 48 hr to prepare AlPO-18 molecular sieve membrane with gas separating performance and CO content under 0.1MPa pressure difference 2 The permeation rate was 4.2X 10 -6 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The separation selectivity was 90. Literature [ Zhan T Q, Wu T, Shi Y, et al. infiluence of synthesis parameters on prediction of AlPO-18 membranes by single DIPEA for CO 2 /CH 4 separation[J].Journal of Membrane Science,2020,601,117853.]In the method, after the gel is aged for 24 hours, the gel is subjected to hydrothermal reaction at 160 ℃ for 15 hours to prepare CO 2 /CH 4 An AlPO-18 molecular sieve membrane with a selectivity of 56 is ideal. The current method takes longer time, needs longer reaction time or aging time, and therefore needs to develop a method for preparing the AlPO-18 molecular sieve membrane which takes shorter time.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provides a method for preparing an AlPO-18 molecular sieve membrane with high acceleration of alcohol, and the obtained membrane has good gas separation performance. The purpose of the invention is realized based on the following technical scheme:
in a first aspect of the invention, a method for preparing an AlPO-18 molecular sieve membrane by alcohol acceleration comprises the following steps:
s1, preparation of seed crystal: mixing an aluminum source, a phosphorus source and water to form uniform gel, adding N, N-Diisopropylethylamine (DIPEA), stirring and aging at room temperature for 2-8 h, performing hydrothermal crystallization at 140-180 ℃ for 1-6 h to obtain crystals, washing, and drying to obtain AlPO-18 molecular sieve seed crystals;
s2, preparing membrane synthesis gel: uniformly mixing an aluminum source, a phosphorus source, N-diisopropylethylamine, deionized water and alcohol, stirring at room temperature, and aging for 2-8 hours to obtain uniform gel;
s3, pretreatment of the support: loading the seed crystal obtained in the step S1 on the surface of the pretreated porous support body to obtain a seed crystal support body, wherein the pore diameter of the porous support body is 2-3 um;
s4, membrane synthesis: placing the seed crystal support body in a stainless steel reaction kettle filled with the gel synthesized in the step S2 for hydrothermal crystallization for 3-12 h; and taking out the support body, washing and soaking the support body by using deionized water, and then drying and calcining the support body to obtain the AlPO-18 molecular sieve membrane.
Preferably, the molar ratio n (Al) of the oxides of each species in the synthetic sol in step S1 2 O 3 ):n(P 2 O 5 ):n(DIPEA):n(H 2 O)＝1:[0.8,1.2]:[1,3]:[50,80](ii) a And/or the room-temperature stirring and aging time is 2-8 h, the hydrothermal crystallization temperature is 140-180 ℃, and the hydrothermal crystallization time is 1-12 h.
Preferably, the aluminum source in the step S1 and the step S2 is aluminum powder, aluminum hydroxide, aluminum isopropoxide or aluminum sec-butoxide, and the phosphorus source is phosphoric acid.
Preferably, the alcohol in step S2 is methanol, ethanol or isopropanol.
Preferably, the molar ratio n (Al) of each species in the synthetic sol in step S2 2 O 3 ):n(P 2 O 5 ):n(DIPEA):n(H 2 O n (alcohol) 1: [0.8,1.2]:[0.8,1.5]:[60,200]:(0,4]。
Preferably, the support in step S3 is symmetric alpha-Al 2 O 3 Asymmetric alpha-Al 2 O 3 And/or the pretreatment is to cut the support body into a certain length, then to wash with deionized water, to clean with ultrasonic wave, and to dry at 70-120 ℃.
Preferably, the crystallization temperature in step S4 is 140-180 ℃.
Preferably, the drying temperature in the step S4 is 80-100 ℃, and/or the calcining temperature is 400-550 ℃.
In a second aspect of the invention, an AlPO-18 molecular sieve membrane is provided, characterized in that it is prepared according to any one of the above preparation methods.
In a third aspect of the invention, there is provided AlSeparation of CO by PO-18 molecular sieve membrane 2 /CH 4 Mixture or separation of N 2 /CH 4 The use in mixtures.
The invention can obtain at least one of the following beneficial effects:
the method adds alcohol into the initial gel to prepare the AlPO-18 molecular sieve membrane, can shorten the synthesis time of the AlPO-18 molecular sieve membrane in actual operation, has simple and convenient operation steps, and ensures that the obtained molecular sieve membrane has good CO 2 /CH 4 And N 2 /CH 4 Separation performance. In the synthesis process, a seed crystal induction secondary growth method is adopted, so that the seed crystal can be synthesized in a short time, and the preparation time of the seed crystal is shortened; the gel is prepared by using an aluminum source, a phosphorus source, N-diisopropylethylamine, deionized water and alcohol, so that the synthesis time of the gel synthesized by the membrane and the hydrothermal crystallization time of the AlPO-18 molecular sieve membrane on the support body are shortened. For a porous support body with a larger aperture, the molecular sieve is easy to fall into the pores of the carrier and cannot grow well; the invention uses alcohol to accelerate the crystal to grow well on the porous support with larger aperture, and prepares the continuous compact AlPO-18 molecular sieve membrane.
By the method, the AlPO-18 molecular sieve membrane with good gas separation performance is obtained; CO of AlPO-18 molecular sieve membrane under the pressure difference of 0.1MPa 2 /CH 4 And N 2 /CH 4 The ideal selectivity reaches 116 and 6.9 respectively, and CO 2 、N 2 Respectively, about (9.31 and 0.55). times.10 -7 mol/(m 2 ·s·Pa)。
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of AlPO-18 molecular sieve membranes prepared in examples 1, 5 and 6: (a) methanol, (b) ethanol, (c) isopropanol;
FIG. 2 is a surface Scanning Electron Microscope (SEM) image of the AlPO-18 molecular sieve membranes prepared in examples 1, 5 and 6: (a) methanol, (b) ethanol, (c) isopropanol; cross-sectional Scanning Electron Microscope (SEM) images: (a ') methanol, (b ') ethanol, (c ') isopropanol;
FIG. 3 is an XRD spectrum of the AlPO-18 molecular sieve prepared in example 1;
FIG. 4 is an SEM image of the AlPO-18 molecular sieve prepared in example 1;
FIG. 5 is an XRD spectrum of an AlPO-18 molecular sieve membrane prepared in comparative example 1.
FIG. 6 is a surface SEM image (left) and a cross-sectional SEM image (right) of an AlPO-18 molecular sieve membrane prepared in comparative example 1;
FIG. 7 shows the dispersion of the templating agent in water: (a) deionized water, (b) deionized water + DIPEA, (c) deionized water + DIPEA and alcohol.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing seed crystals: 40g of gel is synthesized by respectively using aluminum isopropoxide as an aluminum source, phosphoric acid as a phosphorus source and N, N-Diisopropylethylamine (DIPEA) as a template agent. Mixing and stirring aluminum isopropoxide and ultrapure water for 1h, dropwise adding phosphoric acid and stirring for 1h, continuously dropwise adding N, N-diisopropylethylamine, and aging for 6h to form uniform and stable sol; the molar ratio of the sol system is 1Al 2 O 3 :1P 2 O 5 :2DIPEA:60H 2 O。
Pouring the aged sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal synthesis for 4h at 160 ℃, taking out the reaction kettle after the reaction is finished, rapidly cooling the reaction kettle in flowing cold water, centrifugally cleaning the obtained product with ultrapure water, drying the product in a 100 ℃ oven for 12h, taking out the seed crystal, and grinding the seed crystal for later use. The crystals prepared were characterized by XRD and SEM as shown in fig. 1 and 2, respectively.
FIG. 1 is the XRD diffractogram of the synthesized seed crystals, from which it can be seen that the prepared molecular sieve is phase-pure AlPO-18 crystals. Fig. 2 is an SEM image of the synthesized seed crystal, from which it can be seen that the morphology of the synthesized seed crystal is hexagonal.
(2) Pretreatment of the support body: making a symmetrical tubular alpha-Al with the aperture of 2-3 um 2 O 3 And (2) cutting the support body into 6.5cm, repeatedly ultrasonically cleaning the support body by using deionized water for a plurality of times, drying the support body in an oven, and wiping the seed crystal prepared in the step (1) on the surface of the support body to form a seed crystal layer.
(3) Preparing an AlPO-18 molecular sieve membrane: mixing and stirring phosphoric acid and ultrapure water for 10min, slowly adding aluminum isopropoxide, and stirring for 1h until the aluminum isopropoxide is dissolved; uniformly mixing isopropanol and N, N-diisopropylethylamine, and dropwise adding the mixture to Al 2 O 3 -P 2 O 5 -H 2 Aging in O solution for 6h to form uniform and stable sol, wherein the molar ratio of the synthesized gel is 1Al 2 O 3 :1P 2 O 5 :1DIPEA:120H 2 O:1IPA。
Putting the seed crystal support body into a stainless steel reaction kettle filled with the synthetic gel, and carrying out hydrothermal reaction for 12 hours in a preheated oven with the temperature of 160 ℃. Taking out the reaction kettle, spraying the reaction kettle to room temperature under cold water, taking out the support body, washing off the gel attached to the surface by using deionized water, soaking the support body in the deionized water for 1 day, and drying. Calcining at 480 ℃ for 8h to remove the organic template agent to obtain the product AlPO-18 molecular sieve membrane.
The prepared molecular sieve membrane is characterized by XRD and SEM, and is respectively shown in figure 1(c) and figure 2(c, c'), and the molecular sieve membrane synthesized under the condition has good cross-linking property and continuous and compact molecular sieve membrane layer. At 25 deg.C and feeding pressure of 0.1MPa, subjecting it to CO 2 And CH 4 P is the single gas permeation quantity and is expressed in mol/(m) 2 S.pa) S is the ratio of the single gas permeances and represents the ideal selectivity of the gas pair. The results are shown in Table 1, CO 2 /CH 4 The ideal selectivity of the catalyst reaches 116, CO 2 The penetration amount of (2) was 9.31X 10 -7 mol/(m 2 ·s·Pa)。
Example 2
The difference from the example 1 is that the molar ratio of the synthesized gel in the molecular sieve membrane synthetic fluid is 1Al 2 O 3 :1P 2 O 5 :1DIPEA:120H 2 2IPA as the O component, and the synthesis time of the molecular sieve membrane is 10 h. The rest is the same as example 1.
The prepared molecular sieve membrane is characterized by XRD and SEM, and the result shows that the molecular sieve membrane layer is continuous and compact and has good crosslinking performance. At 25 ℃ and 0.1MPa differential pressure for CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
Example 3
The difference from example 1 is that: the molar ratio of the synthesized gel in the molecular sieve membrane synthetic solution is 1Al 2 O 3 :1P 2 O 5 :1DIPEA:120H 2 3IPA as the O component, and the synthesis time of the molecular sieve membrane is 6 h. The rest is the same as example 1.
The prepared molecular sieve membrane is characterized by XRD and SEM, and the result shows that the molecular sieve membrane layer is continuous and compact and has good crosslinking performance. At 25 ℃ and 0.1MPa differential pressure for CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
Example 4
The difference from the example 1 is that the molar ratio of the synthesized gel in the molecular sieve membrane synthetic fluid is 1Al 2 O 3 :1P 2 O 5 :1DIPEA:120H 2 4IPA, the synthesis time of the molecular sieve membrane is 6 h. The rest is the same as example 1.
The prepared molecular sieve membrane is characterized by XRD and SEM, and the result shows that the molecular sieve membrane layer is continuous and compact and has good crosslinking performance. At 25 ℃ and 0.1MPa differential pressure for CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
Example 5
The difference from example 1 is that methanol is used as the alcohol in the raw material of the molecular sieve membrane synthesis solution, and the rest is the same as example 1.
The prepared molecular sieve membrane is characterized by XRD and SEM, and is respectively shown in figure 1(a) and figure 2(a, a'). The results show that the molecular sieve membrane layer is continuous and compact and has good crosslinking performance. As the methanol acceleration effect is more obvious than that of isopropanol, heterogeneous AFI crystals appear on the surface of the film layer. Under the pressure difference of 0.1MPa and the temperature of 25 ℃,to CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
Example 6
The difference from the example 1 is that the alcohol in the raw material of the molecular sieve membrane synthesis solution is ethanol, and the rest is the same as the example 1.
The prepared molecular sieve membrane is characterized by XRD and SEM, and is respectively shown in figure 1(b) and figure 2(b, b'). The result shows that the molecular sieve membrane layer is continuous and compact, the crosslinking performance is good, and a small amount of impure phase AFI crystals appear on the surface of the membrane layer due to the obvious acceleration effect of ethanol compared with isopropanol. At 25 ℃ and 0.1MPa differential pressure for CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
Comparative example 1
The steps (1) and (2) are the same as in example 1, except that:
(3) preparing an AlPO-18 molecular sieve membrane: mixing phosphoric acid and ultrapure water, stirring for 10min, slowly adding aluminum isopropoxide, stirring for 1h until the aluminum isopropoxide is dissolved, and dropwise adding N, N-diisopropylethylamine to Al 2 O 3 -P 2 O 5 -H 2 Aging in O solution for 6h to form uniform and stable sol, and synthesizing gel with molar ratio of 1Al 2 O 3 :1P 2 O 5 :1DIPEA:120H 2 O。
Putting the seed crystal support body into a stainless steel reaction kettle filled with the synthetic gel, and carrying out hydrothermal reaction for 15h in a preheated oven with the temperature of 160 ℃. Taking out the reaction kettle, spraying the reaction kettle to room temperature under cold water, taking out the support body, washing off the gel attached to the surface by using deionized water, soaking the support body in the deionized water for one day, and drying the support body. Calcining at 480 ℃ for 8h to remove the organic template agent to obtain the product AlPO-18 molecular sieve membrane.
FIG. 5 is an XRD diffraction pattern of the synthesized AlPO-18 molecular sieve membrane, from which it can be seen that the synthesized product is the AlPO-18 molecular sieve membrane. FIG. 6 is the surface and cross-sectional electron microscope image of the synthesized AlPO-18 molecular sieve membrane. The results show that the support surface is a continuous dense molecular sieve membrane layer. At 25 ℃ and 0.1MPa differential pressure for CO 2 、N 2 ，CH 4 The single gas permeability was tested and the single gas flux and ideal selectivity for gas pairs are shown in table 1.
TABLE 1
Note: the test was carried out at 25 ℃ and a feed pressure of 0.1 MPa.
As can be seen from the data in Table 1, the AlPO-18 molecular sieve membrane with high gas permeability can be synthesized by introducing alcohol as a solvent into the synthesis gel. The AlPO-18 molecular sieve membrane prepared by hydrothermal reaction of the synthetic fluid without adding alcohol at 160 ℃ for 15h has 68 CO 2 /CH 4 Ideal selectivity; after isopropanol is added, the hydrothermal reaction is carried out for 12 hours at 160 ℃, and then CO can be prepared 2 /CH 4 An AlPO-18 molecular sieve membrane with ideal selectivity reaching 116; with increasing alcohol usage, the hydrothermal reaction time can be further shortened and still achieve a separation effect similar to or even superior to that of comparative example 1. CO can be prepared under the same conditions after isopropanol is replaced by methanol and ethanol 2 /CH 4 The ideal AlPO-18 molecular sieve membrane with selectivity of 64 and 78 shortens the hydrothermal reaction time to a certain extent and improves the separation performance.
FIG. 7 shows a comparison of the dispersion of the templating agent without and after addition of alcohol. Pure DIPEA was added to the deionized water, and as shown in fig. 7(b), the liquid level was observed to stratify; this is because the templating agent is oily and too much templating agent does not readily access the reaction during hydrothermal synthesis. As shown in fig. 7(c), after the alcohol is added to DIPEA, the membrane synthesis reaction solution can be better dispersed in water, i.e., the membrane synthesis reaction solution can be in a uniform state, so that the template agent can better participate in the reaction.
Example 7
And (3) repeatability test: the procedure of example 1 was repeated 4 times to obtain different AlPO-18 molecular sieve membranes with the single gas flux and the desired selectivity of the gas pair as shown in Table 2.
TABLE 2
Note: the test is carried out at 25 ℃ and a feed pressure of 0.1 MPa. CO 2 2 /CH 4 The data in parentheses below are the CO at the corresponding selectivities 2 The ratio of the active ingredients to the total amount of the active ingredients.
The experimental results prove that in the separation process, CO 2 The proportion of the AlPO-18 molecular sieve membrane is kept in a certain range, and the difference is very small, which indicates that the AlPO-18 molecular sieve membrane has good repeatability under the reaction condition.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. The method for preparing the AlPO-18 molecular sieve membrane by alcohol acceleration is characterized by comprising the following steps of:
s1, preparation of seed crystal: mixing an aluminum source, a phosphorus source and water to form uniform gel, adding N, N-diisopropylethylamine, stirring and aging at room temperature for 2-8 h, performing hydrothermal crystallization at 140-180 ℃ for 1-6 h to obtain crystals, washing, and drying to obtain AlPO-18 molecular sieve seed crystals;
s2, preparing membrane synthesis gel: uniformly mixing an aluminum source, a phosphorus source, N-diisopropylethylamine, deionized water and alcohol, stirring at room temperature, and aging for 2-8 hours to obtain uniform gel;
s3, pretreatment of the support: loading the seed crystal obtained in the step S1 on the surface of the pretreated porous support body to obtain a seed crystal support body, wherein the pore diameter of the porous support body is 2-3 um;
s4, membrane synthesis: placing the seed crystal support body in a stainless steel reaction kettle filled with the gel synthesized in the step S2 for hydrothermal crystallization for 3-12 h; and taking out the support body, washing and soaking the support body by using deionized water, and then drying and calcining the support body to obtain the AlPO-18 molecular sieve membrane.
2. The method for preparing AlPO-18 molecular sieve membrane with acceleration of alcohol according to claim 1, wherein the molar ratio n (Al) of each oxide species in the synthetic sol in step S1 2 O 3 ):n(P 2 O 5 ):n(DIPEA):n(H 2 O)＝1:[0.8,1.2]:[1,3]:[50,80]。
3. The method for preparing the AlPO-18 molecular sieve membrane at the accelerated speed of the alcohol according to claim 1, wherein the aluminum source in the step S1 and the step S2 is aluminum powder, aluminum hydroxide, aluminum isopropoxide or aluminum sec-butoxide, and the phosphorus source is phosphoric acid.
4. The method for preparing AlPO-18 molecular sieve membrane at an accelerated speed by using alcohol as claimed in claim 1, wherein the alcohol in step S2 is methanol, ethanol or isopropanol.
5. The method for alcohol-accelerated preparation of AlPO-18 zeolite membranes as claimed in claim 1, wherein the molar ratio of each species in the synthetic sol, n (Al), is in step S2 2 O 3 ):n(P 2 O 5 ):n(DIPEA):n(H 2 O n (alcohol) 1: [0.8,1.2]:[0.8,1.5]:[60,200]:(0,4]。
6. The method for preparing AlPO-18 molecular sieve membrane with acceleration of alcohol according to claim 1, wherein the support in step S3 is symmetric alpha-Al 2 O 3 Asymmetric alpha-Al 2 O 3 And/or the pretreatment is to cut the support body into a certain length, then to wash with deionized water, to clean with ultrasonic wave, and to dry at 70-120 ℃.
7. The method for preparing the AlPO-18 molecular sieve membrane at the accelerated speed of the alcohol according to claim 1, wherein the crystallization temperature in the step S4 is 140-180 ℃.
8. The method for preparing the AlPO-18 molecular sieve membrane at an accelerated speed by the alcohol according to claim 1, wherein the drying temperature in the step S4 is 80-100 ℃, and/or the calcining temperature is 400-550 ℃.
9. An AlPO-18 molecular sieve membrane, characterized by being prepared according to the preparation method of any one of claims 1 to 8.
10. The use of an AlPO-18 zeolite membrane according to claim 9 in the separation of CO 2 /CH 4 Mixture or separation of N 2 /CH 4 The use in mixtures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210596788.1A CN114797497A (en) | 2022-05-30 | 2022-05-30 | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210596788.1A CN114797497A (en) | 2022-05-30 | 2022-05-30 | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114797497A true CN114797497A (en) | 2022-07-29 |
Family
ID=82520135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210596788.1A Pending CN114797497A (en) | 2022-05-30 | 2022-05-30 | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114797497A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480620A (en) * | 2009-02-26 | 2009-07-15 | 南京工业大学 | Preparation method of Silicalite-1 molecular sieve membrane catalyst for shape-selective disproportionation of toluene |
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Preparation method for preparing NaA molecular sieve membrane by induction of nano seed crystal |
| CN102826568A (en) * | 2012-09-26 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Preparation method of nanocrystalline ZSM-5 zeolite cluster, and nanocrystalline ZSM-5 zeolite cluster prepared thereby |
| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN105174280A (en) * | 2015-09-30 | 2015-12-23 | 吉林大学 | Nanpsheet-shaped SAPO-34 molecular sieve as well as ultrafast preparation method and application thereof |
| WO2016061727A1 (en) * | 2014-10-20 | 2016-04-28 | 中国科学院大连化学物理研究所 | Method for synthesizing slice-shaped nanometer sapo-34 molecular sieve |
| CN105585022A (en) * | 2014-10-20 | 2016-05-18 | 中国科学院大连化学物理研究所 | Synthetic method of flaky nano-SAPO-34 molecular sieve |
| CN105621452A (en) * | 2016-03-05 | 2016-06-01 | 复旦大学 | Multistage pore ZSM-5 catalyst for preparing acrolein by glycerol dehydration and preparation method of catalyst |
| CN109081358A (en) * | 2018-08-13 | 2018-12-25 | 桂林理工大学 | A kind of method that non-ferrous metal tin ore tailing quickly prepares high-crystallinity ZSM-5 molecular sieve without acidleach removal of impurities |
| CN109806729A (en) * | 2019-04-04 | 2019-05-28 | 江西师范大学 | The preparation method and application of AlPO-18 molecular screen membrane |
| CN109850913A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of support type ultra-thin two-dimension molecular screen membrane |
| CN110407220A (en) * | 2019-08-27 | 2019-11-05 | 中化泉州能源科技有限责任公司 | A kind of fast preparation method of bigger serface SAPO-34 molecular sieve |
-
2022
- 2022-05-30 CN CN202210596788.1A patent/CN114797497A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480620A (en) * | 2009-02-26 | 2009-07-15 | 南京工业大学 | Preparation method of Silicalite-1 molecular sieve membrane catalyst for shape-selective disproportionation of toluene |
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Preparation method for preparing NaA molecular sieve membrane by induction of nano seed crystal |
| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN102826568A (en) * | 2012-09-26 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Preparation method of nanocrystalline ZSM-5 zeolite cluster, and nanocrystalline ZSM-5 zeolite cluster prepared thereby |
| WO2016061727A1 (en) * | 2014-10-20 | 2016-04-28 | 中国科学院大连化学物理研究所 | Method for synthesizing slice-shaped nanometer sapo-34 molecular sieve |
| CN105585022A (en) * | 2014-10-20 | 2016-05-18 | 中国科学院大连化学物理研究所 | Synthetic method of flaky nano-SAPO-34 molecular sieve |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN105174280A (en) * | 2015-09-30 | 2015-12-23 | 吉林大学 | Nanpsheet-shaped SAPO-34 molecular sieve as well as ultrafast preparation method and application thereof |
| CN105621452A (en) * | 2016-03-05 | 2016-06-01 | 复旦大学 | Multistage pore ZSM-5 catalyst for preparing acrolein by glycerol dehydration and preparation method of catalyst |
| CN109850913A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of support type ultra-thin two-dimension molecular screen membrane |
| CN109081358A (en) * | 2018-08-13 | 2018-12-25 | 桂林理工大学 | A kind of method that non-ferrous metal tin ore tailing quickly prepares high-crystallinity ZSM-5 molecular sieve without acidleach removal of impurities |
| CN109806729A (en) * | 2019-04-04 | 2019-05-28 | 江西师范大学 | The preparation method and application of AlPO-18 molecular screen membrane |
| CN110407220A (en) * | 2019-08-27 | 2019-11-05 | 中化泉州能源科技有限责任公司 | A kind of fast preparation method of bigger serface SAPO-34 molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 代校军: "小粒径SAPO-11分子筛合成的研究进展", 《化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Highly permeable and oriented AlPO-18 membranes prepared using directly synthesized nanosheets for CO 2/CH 4 separation | |
| CN112038648B (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
| CN105233702B (en) | A kind of utilization cobalt nano-array layer conversion forms the preparation method of the films of metal organic framework ZIF 67 | |
| Ueno et al. | High-performance silicalite-1 membranes on porous tubular silica supports for separation of ethanol/water mixtures | |
| Tian et al. | Synthesis of a SAPO-34 membrane on macroporous supports for high permeance separation of a CO 2/CH 4 mixture | |
| CN101112676A (en) | Two-step home-position hydrothermal synthesis of molecular sieve film | |
| CN109201109B (en) | Catalyst for preparing olefin from methanol and preparation method thereof | |
| EP3253474A1 (en) | Pervaporation and vapor-permeation separation of gas-liquid mixtures and liquid mixtures by sapo-34 molecular sieve membrane prepared in dry-gel process | |
| CN110627491B (en) | Synthesis method of molecular sieve membrane with sandwich structure and application of membrane | |
| CN113070056A (en) | General synthesis method of tantalum pentoxide photocatalytic material with three-dimensional ordered network structure | |
| US20200306700A1 (en) | Zeolite membrane complex and method of producing zeolite membrane complex | |
| Wang et al. | Sustainable synthesis of highly water-selective ZSM-5 membrane by wet gel conversion | |
| Xia et al. | The influence of nanoseeds on the pervaporation performance of MFI-type zeolite membranes on hollow fibers | |
| Ueno et al. | Fabrication of pure-silica* BEA-type zeolite membranes on tubular silica supports coated with dilute synthesis gel via steam-assisted conversion | |
| Luo et al. | Recent advances in acid-resistant zeolite T membranes for dehydration of organics | |
| CN103011196A (en) | Method for synthesizing SAPO-41 (Phosphoric Acid Silicon-Aluminum-41) molecular sieve by adopting novel template agent | |
| CN1128004C (en) | Microwave heating to synthesize molecular sieve film | |
| CN113600175A (en) | General synthesis method of three-dimensional ordered macroporous structure sodium tantalate photocatalytic hydrogen production material | |
| CN104192860B (en) | A kind of synthetic method of lamelliform pattern SAPO-34 molecular sieve | |
| CN103043681A (en) | Preparation method of nano layered ZSM (Zeolite Molecular Sieve)-5 zeolite molecular sieve | |
| CN114797497A (en) | Method for preparing AlPO-18 molecular sieve membrane by alcohol acceleration and application | |
| CN111137904A (en) | CHA type molecular sieve and synthesis method and application thereof | |
| CN109734103A (en) | Synthesize the method with the SAPO-34 molecular sieve of multi-stage artery structure | |
| CN115043431A (en) | General synthesis method of pyrochlore type potassium tantalate photocatalytic material with three-dimensional ordered macroporous structure | |
| US11534725B2 (en) | Zeolite membrane complex and method of producing zeolite membrane complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |